160401-91-2Relevant academic research and scientific papers
Dinitrogenvanadates(-1): Synthesis, Reactions and Conditions for their Stability
Gailus, Hartmut,Woitha, Claus,Rehder, Dieter
, p. 3471 - 3478 (2007/10/02)
Reduction of by Na or Li (M) in the presence of phosphines (Lm) and N2 yielded the complexes Na (n = 1 or 2), M2(4-n)> 2 = Me2PCH2CH2PMe2 (dmpe) or Ph2PCH2CH2PPh2>, Na3> 3 = PhP2, MeP2 (bdmpm) or MeP2> and Na4> 4 = P3, P3 or P3>.Generally, the complexes are labile, with a maximum stability for cis- and trans-M.In the presence of CO or CN-t-Bu, N2 is replaced by these ligands.The compounds have been characterized by their ν(NN) pattern and by 51V; 23Na and 7Li NMR spectroscopy.The 51 V NMR spectra exhibit well resolved multiplets.All spectroscopic data, in particular 7Li NMR of cis- and trans- in tetrahydrofuran, are indicative of close contact ion-pair interaction of the kind V-NN...M(1+).The potassium ion and large cations such as (1+) do not provide stable complexes, and complexation of Li(1+) and Na(1+) by crown ethers leads to immediate decomposition of the N2 complexes.The reductive protonation of part of the co-ordinated N2 to NH4(1+) (plus small amounts of N2H5(1+)) is discussed in term of similar reactivity features to the analogous complexes, and in the context of these N2 complexes as functional models for nitrogenases.The compound , isolated as an intermediate product of the reduction of VCl3, reacted with LiNHNH2 to yield ammonia.
